Kinetics and fractionation of carbon and oxygen isotopes during the solid-phase transformation of biogenic aragonite to calcite: The effect of organic matter

Abstract

The phase transformation of biogenic shells from aragonite to calcite can modify the primary carbon and oxygen isotopic values (δ13C and δ18O), and thus affect their significance as paleoenvironmental proxies. While the biasing of δ13C and δ18O by dissolution and reprecipitation phase transformation (DR) has been extensively studied, thermal solid-phase transformation (SPT) in archaeological shell middens is rarely considered. In this study, the effects of intra-crystalline organic matter on the kinetics and carbon and oxygen isotopic fractionation during thermal SPT are evaluated by comparing two sets of experiments on powdered aragonite snail shells heated in air and pure nitrogen atmospheres. The results show that during heating temperature below 400 °C, the intra-crystalline organic matter could inhibit the phase transformation due to the shielding effect of organic matter, while during heating temperature above 400 °C, the decomposition of the intra-crystalline organic matter increases the kinetic rate of the phase transformation. The activation energy for the phase transformation was determined to be +150.5 kJ·mol−1, lower than that of +247 kJ·mol−1 obtained for abiogenic polycrystalline aragonite and close to that of +158 to +163 kJ·mol−1 for abiogenic single crystal aragonite. This is attributed to the larger lattice parameter c in biogenic aragonite and the increasing porosity of calcium carbonate with the decomposition of organic matter. In a nitrogen atmosphere, the deviation of δ13C and δ18O between the heated sample (the mixture of aragonite and calcite) and the original shell aragonite (Δ13CM-A and Δ18OM-A) is negligible during heating temperature below 400 °C; however, Δ13CM-A (from −0.43‰ to 0.00‰) and Δ18OM-A (from −1.54‰ to −0.02‰) are significant during heating temperature above 400 °C. The temperature-dependence of Δ13CM-A in biogenic carbonates is much more significant than that in abiogenic carbonates, which clearly reflects the occurrence of isotopic exchange between the intra-crystalline organic matter and the carbonates. In air, the heating-induced calcium carbonate is depleted in δ13C by up to −0.48‰ and in δ18O by up to −3.46‰, compared with the original samples, which is mainly caused by isotopic exchange with the external carbon dioxide in air and the intra-crystalline organic matter, with the latter being the dominant source. Our results demonstrate that the decomposition of the intra-crystalline organic matter increases the kinetic rate and induces carbon and oxygen isotope fractionation during SPT from aragonite to calcite. This study provides direct evidence for evaluating the preservation of carbon and oxygen isotopes of biogenic calcium carbonate shells which have undergone the SPT process in archaeological shell middens.